Negative electrode active material, negative electrode including the same and lithium secondary battery including the same

ABSTRACT

The present invention relates to a negative electrode active material which includes a secondary particle including a first particle which is a primary particle, wherein the first particle includes a first core and a first surface layer which is disposed on a surface of the first core and contains carbon, and the first core includes a metal compound which includes one or more of a metal oxide and a metal silicate and one or more of silicon and a silicon compound; a method of preparing the same; an electrode including the same; and a lithium secondary battery including the same.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of U.S. application Ser. No.15/771,168, filed Apr. 26, 2018, which is the U.S. National Phase ofPCT/KR2017/005785, filed Jun. 2, 2017, and which claims priority to andthe benefit of Korean Patent Application No. 10-2016-0068956, filed onJun. 2, 2016, Korean Patent Application No. 10-2016-0068940, filed onJun. 2, 2016, and Korean Patent Application No. 10-2017-0068856, filedon Jun. 2, 2017 the disclosures of which are incorporated herein byreference in their entirety.

TECHNICAL FIELD

The present invention relates to a negative electrode active material, anegative electrode including the same and a lithium secondary batteryincluding the same.

BACKGROUND ART

With a recent trend of miniaturization and weight lightening ofelectronic devices, miniaturization and weight lightening of batteriesused therein as a power supply also have been also required. Lithiumsecondary batteries are commercialized as batteries that are small,light, chargeable and dischargeable with high capacity, and used inportable electronic devices such as small video cameras, mobile phonesand laptops, communication devices, etc.

Generally, a lithium secondary battery is formed with a positiveelectrode, a negative electrode, a separator and an electrolyte, andcharge and discharge are possible due to lithium ions perform a role oftransferring energy while travelling back and forth between bothelectrodes, for example lithium ions coming out of a positive electrodeactive material and being intercalated into a negative electrode activematerial, that is, carbon particles, by first charge, and deintercalatedagain during discharge.

Further, with the development of portable electronic devices, highcapacity batteries have been continuously required, and research hasbeen actively conducted on high capacity negative electrode materialssuch as tin, silicon or the like having significantly higher capacityper unit weight compared to carbon used currently as negative electrodematerial. Among them, a negative electrode material using silicon hasabout 10 times higher capacity than a negative electrode material usingcarbon.

As a result, research has been conducted on a negative electrodematerial with high capacity using silicon in which there is no damage tothe electrode even when lithium is intercalated and deintercalatedrepeatedly.

PRIOR ART LITERATURE Patent Literature

-   (Patent Literature 1) KR2005-0090218A

DISCLOSURE Technical Problem

The present invention provides a negative electrode active materialwhich can prevent a negative electrode from expanding and contractingdue to an electrochemical reaction between lithium ions, which aredischarged from a positive electrode during charging and discharging oflithium secondary batteries, and silicon, which are included in anegative electrode.

The present invention provides a negative electrode active materialhaving many paths through which lithium ions can move.

The present invention provides a lithium secondary battery having highcapacity and high output characteristics.

The present invention provides a lithium secondary battery which canincrease initial efficiency and has improved rate capability.

Technical Solution

According to an embodiment of the present invention, there is provided anegative electrode active material which includes a secondary particleincluding a first particle which is a primary particle, wherein thefirst particle includes a first core, and a first surface layer which isdisposed on a surface of the first core and contains carbon, and thefirst core includes one or more of silicon and a silicon compound; and ametal compound which includes one or more of a metal oxide and a metalsilicate.

According to another embodiment of the present invention, there isprovided a negative electrode including the negative electrode activematerial.

According to still another embodiment of the present invention, there isprovided a lithium secondary battery including the negative electrode.

Advantageous Effects

The negative electrode active material according to the presentinvention includes secondary particles including first particles whichare primary particles, and thus paths through which lithium ions canmove are allowed to increase such that output characteristics of alithium secondary battery can be improved, an initial efficiency of thelithium secondary battery is high, and rate capability (charge anddischarge characteristics) can be improved.

Further, according to the present invention, due to pores between theprimary particles, damage to the electrode can be minimized even whenintercalation and deintercalation of lithium ions are repeated and corescontract and expand repeatedly.

Further, according to the present invention, the initial efficiency ofthe battery can be further enhanced because the first core is doped witha metal compound.

Moreover, the first particle including the first core doped with themetal compound and the second particle including the second particleundoped with the metal compound is mixed at a suitable weight ratio, andthereby a battery having high capacity and excellent initial efficiencycan be provided.

DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view showing a cross section of a negativeelectrode active material according to an embodiment of the presentinvention.

FIG. 2 is a schematic view showing a cross section of a negativeelectrode active material according to another embodiment of the presentinvention.

FIG. 3 is a schematic view showing a cross section of a negativeelectrode active material according to still another embodiment of thepresent invention.

FIG. 4 is a schematic view showing a cross section of a negativeelectrode active material according to yet another embodiment of thepresent invention.

FIG. 5 is a schematic view showing a cross section of a negativeelectrode active material according to yet another embodiment of thepresent invention.

FIG. 6 is a schematic view showing a cross section of a negativeelectrode active material according to yet another embodiment of thepresent invention.

FIG. 7 is a graph showing normalized capacity of examples of the presentinvention and comparative examples.

MODES OF THE INVENTION

The terms and words used in this specification and claims should not beinterpreted as limited to commonly used meanings or meanings indictionaries and should be interpreted with meanings and concepts whichare consistent with the technological scope of the invention based onthe principle that the inventors have appropriately defined concepts ofterms in order to describe the invention in the best way.

While the invention has been described with reference to exemplaryembodiments illustrated in accompanying drawings, these should beconsidered in a descriptive sense only, and it will be understood bythose skilled in the art that various alterations and equivalent otherembodiment may be made. Therefore, the scope of the invention is definedby the appended claims.

The negative electrode active material according to an embodiment of thepresent invention may include a secondary particle including a firstparticle which is a primary particle, where the first particle mayinclude a first core, and a first surface layer which is disposed on asurface of the first core and contains carbon, and the first core mayinclude one or more of silicon and a silicon compound; and a metalcompound which includes one or more of a metal oxide and a metalsilicate.

FIG. 1 is a schematic view showing a cross section of a negativeelectrode active material according to an embodiment of the presentinvention.

Referring to FIG. 1, the negative electrode active material includes asecondary particle 200 including first particles 110 which are primaryparticles. Here, the term “secondary particle” refers to a particleformed by aggregation of primary particles.

The first particle 110 may include a first core 111 and a first surfacelayer 112.

The first core 111 may include one or more of silicon and a siliconcompound; and a metal compound 113.

Since the silicon has a theoretical capacity of about 3,600 mAh/g, thesilicon has a very high capacity compared to existing negative electrodeactive material including graphite, and thus the capacity of a lithiumsecondary battery including the silicon can be improved.

The silicon compound refers to a compound containing silicon, and may bea silicon oxide (SiO_(x), 0<x<2) in which silicon is dispersed in asilicon dioxide (SiO₂), a Si—C physically or chemically combined with acarbon-based material, or a silicon alloy (Si-alloy) combined with ametal, and specifically may be a silicon oxide (SiO_(x), 0<x<2), andmore specifically may be SiO (0<x≤1), for example, SiO.

When the silicon oxide (SiO_(x), 0<x<2) is included in the first core111, since the silicon oxide (SiO_(x), 0<x<2) has less volume expansionduring intercalation and deintercalation of lithium ions due to chargingand discharging of a lithium secondary battery compared to silicon, itis possible to reduce damage to a negative electrode active material,and to realize high capacity and high initial efficiency which areeffects of the silicon.

The silicon in the silicon oxide (SiO_(x), 0<x≤1) may be amorphous orcrystalline. When the silicon in the silicon oxide (SiO_(x), 0<x≤1) iscrystalline, a crystal size may be more than 0 to 30 nm or less. Whenthe above-described range is satisfied, a lithium secondary battery as afinal product can have a higher capacity than an existing lithiumsecondary battery including graphite, and have the improved initialefficiency.

The first cores 111 may each be a porous core including a plurality ofpores. The porous core increases the contact area between an electrolyteand an electrode such that lithium ions can be rapidly diffused.

When the first core 111 is a porous core, an internal porosity of thefirst core 111 may be in the range of 5 to 90% based on the total volumeof the first core 111. Here, the porosity refers to a “pore volume perunit mass/specific volume+pore volume per unit mass,” and may bemeasured by mercury porosimetry or Brunauer-Emmett-Teller (BET)measurement method. When the above-described range is satisfied, thevolume expansion of the first core 111 during charging and dischargingcan be suppressed, mechanical strength is excellent, and durabilitycapable of withstanding the manufacturing process of a battery such asroll pressing can be attained.

The average particle size D₅₀ of the first core 111 may be in the rangeof 0.5 to 20 μm, and specifically may be in the range of 0.5 to 5 μm.When the average particle size D₅₀ of the first core 111 is in the rangeof 0.5 to 20 μm, aggregation is easy in forming the secondary particle,sintering does not occur even when charging and discharging arerepeated, and thus cracking of a negative electrode can be prevented.Further, a change in volume during charging and discharging can beeffectively prevented. Moreover, the exterior of the electrode can besmoothly formed, and thus an active material layer can be smoothlyroll-pressed during the production of the electrode. Accordingly, anenergy density per unit volume can be improved. In the presentspecification, the average particle size D₅₀ can be defined as aparticle size on the basis of 50% of the particle size distribution ofparticles. The average particle size D₅₀ may be measured using, forexample, a laser diffraction method. The laser diffraction methodgenerally enables measurement of a particle size of several millimetersto submicronic levels, such that results with high reproducibility andhigh resolvability can be obtained.

The BET specific surface area of the first core 111 may be in the rangeof 0.5 to 30 m²/g.

The metal compound 113 may be formed by oxidation of a metal having areducing power capable of reducing a silicon compound, specifically,silicon dioxide (SiO₂) in the silicon compound to silicon. The metalcompound 113 may include one or more of a metal oxide and a metalsilicate.

The metal oxide may include an oxide of one or more metals selected fromthe group consisting of lithium (Li), magnesium (Mg), aluminum (Al),calcium (Ca), and titanium (Ti). Specifically, the metal oxide may beone or more of MgO, MgSi₃ and Mg₂SiO₄.

The metal silicate may include a silicate of one or more metals selectedfrom the group consisting of lithium (Li), magnesium (Mg), aluminum(Al), calcium (Ca) and titanium (Ti).

The metal compound may be formed of a metal with which the first core isdoped. When the first core is doped with the metal, the SiO₂ matrix inSiO can be reduced and a metal compound can be formed. Accordingly,since the content of SiO₂, which causes initial irreversible reaction,can be reduced, the initial efficiency of the battery can be improved.

The weight of the metal compound 113 may be in the range of 1 to 50 wt%, and specifically in the range of 2 to 50 wt % based on the totalweight of the first particle. When the above-described range issatisfied, initial efficiency can be effectively improved, an excessamount of heat is not generated during the reduction reaction of SiO₂,and the crystal size of Si can thus be prevented from becomingexcessively large. Further, most of the doped metals participate in thereaction, and thereby metal impurities may not be generated.

The first surface layer 112 may contain carbon and may be disposed onthe surface of the first core 111. The first surface layer 112 preventsadditional oxidation of the surface of the first core 111. The firstsurface layer 112 may form a conductive path in the negative electrodeactive material to improve the electrical conductivity of the negativeelectrode active material. The first surface layer 112 increases thecapacity per unit volume of the first particle 110, and thereby highcapacity can be exhibited.

The carbon may be amorphous carbon or crystalline carbon. When theamorphous carbon is included in the first surface layer 112, thestrength between the first surface layers 112 can be suitably maintainedsuch that expansion of the first core 111 can be suppressed. When thecrystalline carbon is included in the first surface layer 112,conductivity of a negative electrode active material can be furtherimproved. The crystalline carbon may be fluorene, carbon nanotubes orgraphene.

The first surface layers 112 may each independently include a carbide ofone or more selected from the group consisting of tar, pitch, and otherorganic materials, and specifically, the first surface layers 112 mayeach be independently formed of a tar carbide, a pitch carbide, or acarbide of other organic materials. The carbide of other organicmaterials may be a carbide of an organic material selected from thegroup consisting of sucrose, glucose, galactose, fructose, lactose,mannose, ribose, aldohexose, ketohexose, and combinations thereof.

The first surface layers 112 may each independently include one or morepyrolysis products selected from the group consisting of substituted orunsubstituted aliphatic or alicyclic hydrocarbons, substituted orunsubstituted aromatic hydrocarbons, products obtained in the tardistillation process, vinyl-based resins, phenol-based resins,cellulose-based resins, and pitch-based resins. For example, pyrolysisproducts such as the substituted or unsubstituted aliphatic or alicyclichydrocarbons, substituted or unsubstituted aromatic hydrocarbons, or thelike may be used as a carbon source for chemical vapor deposition.

Specific examples of the substituted or unsubstituted aliphatic oralicyclic hydrocarbons include methane, ethane, ethylene, acetylene,propane, butane, butene, pentane, isobutane, hexane, etc.

Specific examples of the substituted or unsubstituted aromatichydrocarbons include benzene, toluene, xylene, styrene, ethylbenzene,diphenylmethane, naphthalene, phenol, cresol, nitrobenzene,chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene,etc.

Examples of the products obtained in the tar distillation processinclude gas diesel, creosote oil, anthracene oil, naphtha-cracked taroil, etc.

The first surface layer 112 may include a conductive polymer containingcarbon, and the conductive polymer may include one or more selected fromthe group consisting of polycellulose sulfonate, polyacetylene,polyparaphenylene, poly(p-phenylenevinylene), polypyrrole,polythiophene, polyaniline, polyisothianaphthene, polyparamethylene,poly(l-pyrene methyl methacrylate) which is a homopolymer of pyrene,poly(l-pyrene methyl methacrylate-cotriethylene oxide methyl ethermethacrylate) which is a copolymer of pyrene, a polymer obtained bychanging a pyrene side chain of the pyrene homopolymer or copolymer toan anthracene, a polymer having a carbonyl group and methyl benzoicester, and a polyacetylene having a conjugation bond.

The first surface layer 112 may be included at 2 to 50 parts by weightbased on 100 parts by weight of the first core 111. The thickness ofeach of the first surface layer 112 may be in the range of 20 to 100 nm.When the above-described range is satisfied, the electrical conductivityof the lithium secondary battery can be improved while the conductivepaths of the first cores 111 are maintained.

The average particle size D₅₀ of the first particles 110 may be in therange of 0.502 to 20.2 μm, and specifically in the range of 0.502 to 5.2μm. When the above-described range is satisfied, aggregation for formingthe secondary particle is easy, sintering does not occur even whencharging and discharging are repeated, and a change in size can beprevented. In addition, high output characteristics can be exhibited.

Referring to FIG. 1, the secondary particle 200 is formed by aggregationof the first particles 110, and include pores between the firstparticles 110. The porosity between the first particles 110 is in therange of 2 to 50% based on the total volume of the secondary particle200. When the above-described range is satisfied, a buffer area can beprovided with respect to the volume expansion of the first core 111during charging and discharging, and it is possible to prevent thesecondary particle 200 from being crushed. Further, the moving speed oflithium ions is raised to improve output characteristics.

The definition and measurement method of the porosity between the firstparticles 110 are mentioned in the description of the internal porosityof the porous particles, and thus the description thereof will beomitted.

The average particle size of the secondary particle 200 may be in therange of 2 to 50 μm, and specifically may be in the range of 2 to 42 μm.When the above-described range is satisfied, paths through which lithiumions can move increase, and thus a lithium secondary battery as a finalproduct can exhibit high capacity, high power, high initial efficiency,and excellent rate capability.

A negative electrode active material according to another embodiment ofthe present invention is the same as the above-described negativeelectrode active material according to an embodiment of the presentinvention except that the secondary particle further includes secondparticles which are primary particles. Referring to FIG. 2, thesecondary particle 210 further include second particles 120 which areprimary particles in addition to the first particles 110, the secondparticle 120 includes a second core 121, and a second surface layer 122which is disposed on a surface of the second core 121 and containscarbon, and the second core 121 may include one or more of silicon and asilicon compound. Here, the first particles 110 are the same as thefirst particles described with reference to FIG. 1, and thus adescription thereof will be omitted.

The second particle 120 may include a second core 121 and a secondsurface layer 122.

The second core 121 may include one or more of silicon and a siliconcompound.

Since the silicon has a theoretical capacity of about 3,600 mAh/g, thesilicon has a very high capacity compared to the existing negativeelectrode active material including graphite, and thus the capacity of alithium secondary battery including the silicon can be improved.

The silicon compound refers to a compound containing silicon, and may bea silicon oxide (SiO_(x), 0<x<2) in which silicon is dispersed in asilicon dioxide (SiO₂) matrix, a Si—C physically or chemically combinedwith a carbon-based material, or a silicon alloy (Si-alloy) combinedwith a metal, and specifically may be a silicon oxide (SiO_(x), 0<x<2),and more specifically may be SiO (0<x≤1), for example, SiO.

When the silicon oxide (SiO_(x), 0<x<2) is included in the second core121, since the silicon oxide (SiO_(x), 0<x<2) has less volume expansionduring intercalation and deintercalation of lithium ions due to chargingand discharging of a lithium secondary battery than silicon, it ispossible to reduce damage to a negative electrode active material and torealize high capacity and high initial efficiency which are effects ofthe silicon.

The silicon in the silicon oxide (SiO_(x), 0<x≤1) may be amorphous orcrystalline. When the silicon in the silicon oxide (SiO_(x), 0<x≤1) iscrystalline, a crystal size may be more than 0 to 30 nm or less. Whenthe above-described range is satisfied, a lithium secondary battery as afinal product can have a higher capacity than an existing lithiumsecondary battery including graphite, and have the improved initialefficiency.

The second core 121 may each be a porous core including a plurality ofpores. The porous core increases the contact area between an electrolyteand an electrode such that lithium ions can be rapidly diffused.

When the second core 121 is a porous core, an internal porosity of thesecond core 121 may be in the range of 5 to 90% based on the totalvolume of the second core 121. Here, the porosity refers to a “porevolume per unit mass/specific volume+pore volume per unit mass”, and maybe measured by a mercury porosimetry or Brunauer-Emmett-Teller (BET)measurement method. When the above-described range is satisfied, thevolume expansion of the second core 121 during charging and dischargingcan be suppressed, mechanical strength is excellent, and durabilitycapable of withstanding the manufacturing process of a battery such asroll pressing can be attained.

The average particle size D₅₀ of the second core 121 may be in the rangeof 0.5 to 20 μm, and specifically may be in the range of 0.5 to 5 μm.When the average particle size D₅₀ of the second core 121 is in therange of 0.5 to 20 μm, aggregation is easy in forming the secondaryparticle, sintering does not occur even when charging and dischargingare repeated, and thus cracking of a negative electrode can beprevented. Further, a change in volume during charging and dischargingcan be effectively prevented. Moreover, the exterior of the electrodecan be smoothly formed, and thus an active material layer can besmoothly roll-pressed during the production of the electrode.Accordingly, an energy density per unit volume can be improved.

The BET specific surface area of the second core 121 may be in the rangeof 0.5 to 30 m²/g.

The second surface layer 122 may contain carbon and may be disposed onthe surface of the second core 121. The second surface layer 122prevents additional oxidation of the surface of the second core 121. Thesecond surface layer 122 may form a conductive path in the negativeelectrode active material to improve the electrical conductivity of thenegative electrode active material. The second surface layer 122increases the capacity per unit volume of the second particle 120, andthereby high capacity can be exhibited.

The carbon may be amorphous carbon or crystalline carbon. When theamorphous carbon is included in the second surface layer 122, thestrength between the second surface layers 122 can be suitablymaintained such that expansion of the second core 121 can be suppressed.When the crystalline carbon is included in the second surface layer 122,conductivity of a negative electrode active material can be furtherimproved. The crystalline carbon may be fluorene, carbon nanotubes, orgraphene.

The second surface layer 122 may each independently include a carbide ofone or more selected from the group consisting of tar, pitch and otherorganic materials, and specifically, the second surface layer 122 mayeach be independently formed of a tar carbide, a pitch carbide, or acarbide of other organic materials. The carbide of other organicmaterials may be a carbide of an organic material selected from thegroup consisting of sucrose, glucose, galactose, fructose, lactose,mannose, ribose, aldohexose or ketohexose carbides, and combinationsthereof.

The second surface layer 122 may each independently include one or morepyrolysis products selected from the group consisting of substituted orunsubstituted aliphatic or alicyclic hydrocarbons, substituted orunsubstituted aromatic hydrocarbons, products obtained in the tardistillation process, vinyl-based resins, phenol-based resins,cellulose-based resins, and pitch-based resins. For example, pyrolysisproducts such as the substituted or unsubstituted aliphatic or alicyclichydrocarbons, substituted or unsubstituted aromatic hydrocarbons or thelike may be used as a carbon source for chemical vapor deposition.

Specific examples of the substituted or unsubstituted aliphatic oralicyclic hydrocarbons include methane, ethane, ethylene, acetylene,propane, butane, butene, pentane, isobutane, hexane, etc.

Specific examples of the substituted or unsubstituted aromatichydrocarbons include benzene, toluene, xylene, styrene, ethylbenzene,diphenylmethane, naphthalene, phenol, cresol, nitrobenzene,chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene,etc.

Examples of the products obtained in the tar distillation processinclude gas diesel, creosote oil, anthracene oil, naphtha-cracked taroil, etc.

The second surface layer 122 may include a conductive polymer containingcarbon, and the conductive polymer may include one or more selected fromthe group consisting of polycellulose sulfonate, polyacetylene,polyparaphenylene, poly(p-phenylenevinylene), polypyrrole,polythiophene, polyaniline, polyisothianaphthene, polyparamethylene,poly(l-pyrene methyl methacrylate) which is a homopolymer of pyrene,poly(l-pyrene methyl methacrylate-cotriethylene oxide methyl ethermethacrylate) which is a copolymer of pyrene, a polymer obtained bychanging a pyrene side chain of the pyrene homopolymer or copolymer toan anthracene, a polymer having a carbonyl group and methyl benzoicester, and a polyacetylene having a conjugation bond.

The second surface layer 122 may be included at 2 to 50 parts by weightbased on 100 parts by weight of the second core 121. The thickness ofeach of the second surface layer 122 may be in the range of 20 to 100nm. When the above-described range is satisfied, the electricalconductivity of the lithium secondary battery can be improved while theconductive paths of the second cores 121 are maintained.

The average particle size D₅₀ of the second particle 120 may be in therange of 0.502 to 20.2 μm, and specifically in the range of 0.502 to 5.2μm. When the above-described range is satisfied, aggregation for formingthe secondary particle is easy, sintering does not occur even whencharging and discharging are repeated, and a change in size can beprevented. In addition, high output characteristics can be exhibited.

In the negative electrode active material of the present embodimentdescribed with reference to FIG. 2, although the first particles 110have a larger mass than the second particles 120, the charge anddischarge characteristics of the battery can be improved by doping witha metal during manufacturing. Further, since the second particles 120have a high lithium binding amount, the high capacity characteristics ofthe battery can be improved. Therefore, when the battery includes thenegative electrode including the secondary particle 210 formed by thefirst particles 110 and the second particles 120, both the high capacityand excellent charge and discharge characteristics of the battery can beachieved.

The weight ratio of the first particles 110 and the second particles 120may be in the range of 1:0.25 to 1:4, and specifically, may be in therange of 1:0.43 to 1:1.5. When the weight ratio is satisfied, the highcapacity and excellent charge and discharge characteristics of thebattery can be achieved at a more preferable level, and the effect ofreducing the expansion of the thickness of the electrode can beobtained.

Referring to FIG. 2, the secondary particle 210 is formed by aggregationof the first particles 110 and the second particles 120, and includespores between the first particles 110, pores between the secondparticles 120, and pores between the first particles 110 and the secondparticles 120. The total porosity between the first particles 110,between the second particles 120, and between the first particles 110and the second particles 120 is in the range of 2% to 50% based on thetotal volume of the secondary particle 210. When the above-describedrange is satisfied, a buffer area can be provided with respect to thevolume expansion of the first core 111 and the second core 121 duringcharging and discharging, and it is possible to prevent the secondaryparticle 210 from being crushed. Further, the moving speed of lithiumions is raised to improve output characteristics.

The definition and measurement method of the porosity between the firstparticles 110, the porosity between the second particles 120, and theporosity between the first particles 110 and the second particles 120are mentioned in the description of the internal porosity of the porousparticles, and thus the description thereof will be omitted.

The average particle size of the secondary particle 210 may be in therange of 2 to 50 μm, specifically in the range of 2 to 42 μm, and morespecifically in the range of 4 to 30 μm. When the above-described rangeis satisfied, paths through which lithium ions can move increase, andthus a lithium secondary battery as a final product can exhibit highcapacity, high power, high initial efficiency and excellent ratecapability.

Referring to FIG. 3, the negative electrode active material according tostill another embodiment of the present invention is similar to thenegative electrode active material according to an embodiment of thepresent invention described with reference to FIG. 1, but differs onlyin that the secondary particle 220 includes a carbon layer 130.Accordingly, the carbon layer 130 corresponding to the difference willbe mainly described.

The carbon layer 130 is disposed on the surface of the secondaryparticle, and specifically is disposed on the surface of the structurein which the first particles 110 are aggregated to form the secondaryparticle 220. Due to the carbon layer 130, the expansion of secondaryparticle can be suppressed during charging and discharging and theconductivity of the negative electrode active material can be furtherimproved.

The carbon layer 130 may contain carbon. Specifically, the carbon layer130 may be one or more materials which can form the surface layer 112described above. Further, the carbon layer 130 and the surface layer 112may be formed of the same material, or may be formed of differentmaterial. More specifically, the surface layer and the carbon layer mayall be formed of the above-described carbides of the other organicmaterials, or the surface layer may be a carbide of other organicmaterials, and the carbon layer may be a pitch carbide.

The thickness of the carbon layer 130 may be in the range of 5 to 100nm, and specifically, may be in the range of 10 to 100 nm. When theabove-described range is satisfied, the electrical conductivity of thelithium secondary battery can be improved while maintaining theconductive path between the secondary particles.

The content of the carbon layer may be in the range of 0.1 to 50 wt %,and specifically, in the range of 5 to 25 wt % based on the total weightof the secondary particle. When the above-described range is satisfied,a conductive path for the movement of lithium ions can be secured. Whenthe carbon layer is formed at a level higher than the above-describedrange, the initial efficiency may be excessively decreased.

Referring to FIG. 4, the negative electrode active material according toyet another embodiment of the present invention is similar to thenegative electrode active material according to an embodiment of thepresent invention described with reference to FIG. 2, but differs onlyin that the secondary particle 230 includes a carbon layer 130. Sincethe carbon layer 130 included in the negative electrode active materialof the present embodiment is the same as the carbon layer included inthe negative electrode active material of an embodiment described withreference to FIG. 3, the description thereof will be omitted.

Referring to FIG. 5, the negative electrode active material according toyet another embodiment of the present invention is similar to thenegative electrode active material according to an embodiment of thepresent invention described with reference to FIG. 1, but differs onlyin that the secondary particle 240 includes crystalline carbon-basedmaterials 140. Accordingly, the difference will be mainly described.

The crystalline carbon-based materials 140 may be primary particles.Accordingly, the crystalline carbon-based material 140 aggregates withthe first particles 110 to form the secondary particle 240.Specifically, the crystalline carbon-based materials 140 are mixed withthe first particles 110 in a solvent, and a mixture thereof is dried andcalcined to form a secondary particle structure.

The description of the first particle 110 is as described above.

The crystalline carbon-based material 140 can improve the capacity andcycle characteristics of a lithium secondary battery. Specific examplesof the crystalline carbon-based material 140 include graphene, carbonnanotubes, nanofibers, etc.

The content of the crystalline carbon-based material 140 may be in therange of 75 to 95 parts by weight based on 100 parts by weight of thefirst particles 110. When the above-described range is satisfied, thecapacity and cycle characteristics of the lithium secondary battery as afinal product can be further improved.

Referring to FIG. 6, the negative electrode active material according toyet another embodiment of the present invention is similar to thenegative electrode active material according to an embodiment of thepresent invention described with reference to FIG. 1, but differs onlyin that the secondary particle 250 includes crystalline carbon-basedmaterials 140. Since the crystalline carbon-based materials 140 includedin the secondary particles 250 of the negative electrode active materialof the present embodiment are the same as the crystalline carbon-basedmaterials included in the secondary particles 240 of the negativeelectrode active material of an embodiment described with reference toFIG. 5, the description thereof will be omitted.

The negative electrode active material according to yet anotherembodiment of the present invention is similar to the negative electrodeactive materials of the embodiments described with reference to FIGS. 1to 6, but differs in that the negative electrode active material furtherincludes graphite-based active material particles. The graphite-basedactive material particles may be used together with the secondaryparticles of the above-described embodiments. Specifically, thegraphite-based active material particles may be mixed with the secondaryparticles, and the negative electrode active material may be a mixtureof two types of active materials. Accordingly, the charge and dischargecharacteristics of the battery can be improved. The graphite-basedactive material particle may be one or more selected from the groupconsisting of artificial graphite, natural graphite, graphitized carbonfibers and graphitized mesocarbon microbeads.

The weight ratio of the secondary particles and the graphite-basedactive material particles in the negative electrode active material maybe in the range of 1:1 to 1:49, and specifically, may be in the range of1:9 to 1:19. When the above-described range is satisfied, the charge anddischarge characteristics of the battery are further improved and thepores between the secondary particles can be ensured, such that damageto the electrode can be minimized even when the contraction andexpansion of the secondary particle are repeated. The graphite-basedactive material particles may be mixed together with the preparedsecondary particles in a solvent and used for the production of thenegative electrode.

A method of preparing a negative electrode active material according toyet another embodiment of the present invention includes preparing acore including one or more of silicon or a silicon compound (Step 1);forming a surface layer containing carbon on the surface of the core toform a preliminary first particle (Step 2); forming a first particle bydoping the preliminary first particle with a metal and performing heattreatment (Step 3); and forming a secondary particle including the firstparticles (Step 4). Here, the core includes the first core and thesecond core of the above-described embodiments, the surface layer is thesame as the first surface layer and the second surface layer of theabove-described embodiments, and the first particles are the same as thefirst particles of the above-described embodiments.

In Step 1, the core may be prepared by pulverizing silicon or a siliconcompound having a high average particle size D₅₀ to have an averageparticle size D₅₀ of 0.5 to 20 μm. Specifically, the core may beprepared by introducing a silicon oxide having an average particle sizeD₅₀ of 5 to 50 μm into a bead mill with a zirconia ball and pulverizingin the presence of an ethanol solvent. However, the present invention isnot limited thereto, and the core may be formed of silicon or a siliconcompound obtained by performing heat treatment on a silicon oxide in atemperature range of 1,100° C. or less in an inert gas or reducingatmosphere. Here, the silicon oxide is a general term of an amorphoussilicon oxide obtained by cooling and precipitating silicon monoxide gasproduced by heating a mixture of silicon dioxide and metal silicon.Further, specific examples of the inert gas include Ar, He, H₂, and N₂,and they may be used alone or as a mixed gas. The temperature of theprecipitation plate for cooling and precipitating the silicon monoxidegas may be in the range of 500 to 1,050° C.

Further, the core may be silicon obtained by heating and evaporatingmetallic silicon in a vacuum and precipitating it on a cooling plate.

When the carbon is carbon included in the carbides of the other organicmaterials described above, Step 2 may include Step 2-1 of pulverizing amixture of the core and the other organic materials in a solvent by amilling process and drying, and Step 2-2 of spheroidizing the mixtureand performing heat treatment thereon to carbonize the organic materialto form a surface layer containing carbon on the surface of the core toform a preliminary first particle.

The solvent is not particularly limited as long as the other organicmaterials can be dispersed uniformly, and may be an alcohol such asethanol, n-butanol, 1-propanol, or 2-propanol. The content of theorganic solvent may be in the range of 100 to 300 parts by weight basedon 100 parts by weight of the particles. The milling process isperformed such that the core and the organic materials are pulverized toa desired size, the particles and the organic materials are well mixedin the solvent, and the organic materials are thereby uniformlydistributed on the surface of the particle. The milling process may becarried out using a beads mill, a high energy ball mill, a planetarymill, a stirred ball mill, a vibration mill, etc. Here, the bead mill orthe ball mill may be formed of a chemically inert material which doesnot react with silicon and organic materials, and as a specific example,may be formed of a zirconia material.

The drying may be performed in a temperature range in which the solventcan be evaporated or volatilized, and the temperature range may be inthe range of 60 to 150° C.

Instead of the other organic materials described above, the carbon maybe derived from any of the sources of the surface layer described above.

When the carbon is carbon included in the pyrolysis product, Step 2 maybe a step of forming a surface layer containing carbon on the surface ofthe core by chemical vapor deposition.

When the chemical vapor deposition method is used, the surface layer canbe uniformly formed on the surface of the core.

When the chemical vapor deposition is performed, the temperature may bein the range of 700 to 1,200° C., and a material capable of generatingcarbon by pyrolysis at the above-described temperature is selected asthe carbon source. The carbon source may be one or two or more selectedfrom the group consisting of substituted or unsubstituted aliphatic oralicyclic hydrocarbons, and substituted or unsubstituted aromatichydrocarbons.

When the carbon is carbon included in a conductive polymer, the core maybe dip-coated in a solution containing the conductive polymer to form asurface layer on the core. The description of the conductive polymer isas described above.

Further, the core may be coarse ground in an inert atmosphere to obtaina desired average particle size. Moreover, the mixture of the core andthe other organic materials may further include a crystallinecarbon-based material.

In Step 3, the preliminary first particles may be uniformly mixed withmetal powder in a state in which air is blocked, and then heat-treatedin an argon gas atmosphere in a furnace. Thereafter, the metal powder orthe side reaction material remaining on the particle surface is removedby washing with strong acid or the like. Accordingly, a second particleincluding a core containing a metal compound can be prepared.Specifically, the heat treatment may be performed by raising thetemperature from 900° C. to 1100° C. at a heating rate of 4 to 6°C./min, and then heating for 1 to 3 hours. When doping with a metal andheat treatment are performed before the secondary particles are formed,the metal compound formed by oxidation of the metal may be moreuniformly distributed in the final active material particle compared tothe case in which doping with a metal and heat treatment are performedafter the secondary particles are formed such that the metal compound isincluded in the core.

In Step 4, the first particles are aggregated to form a secondaryparticle. Specifically, when a solution containing the first particlesand the solvent is prepared and the solution is spray-dried, a secondaryparticle in which the first particles aggregate may be formed. Thesolution may further include a carbon precursor to facilitateaggregation of the first particles and the second particles.

The solvent is not particularly limited as long as it allows the firstparticles to be well dispersed, and specific examples thereof includewater, alcohols, N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO),acetonitrile, acetone, tetrahydrofuran (THF), diethyl ether, toluene,1,2-dichlorobenzene, etc.

The inlet temperature during the spray drying may be in the range of 100to 250° C.

The secondary particle may be further subjected to a separatecalcination process for improving durability and conductivity. Thecalcination temperature may be in the range of 400 to 1,000° C.

In Step 4, the secondary particle may be formed by aggregation such thatthe porosity between the first particles is in the range of 2% to 50%.Specifically, in Step 4, a filler is included in the solvent togetherwith the first particles to prepare a solution, and the solution isspray-dried to form a preliminary secondary particle in which the firstparticles and the filler are aggregated.

The filler is included to form a secondary particle such that theporosity between the first particles is in the range of 2% to 50%, andthe porosity may be controlled by adjusting the amount of the filler.The filler may be included in a volume ratio of 1:0.01 to 1:0.43 withrespect to the first particle. Specific examples of the filler include ametal, polymethyl methacrylate (PMMA), polystyrene beads, sodiumchloride (NaCl), potassium chloride (KCl), sodium sulfate (Na₂SO₄), etc.

When the above-described calcination process is included in Step 4, thefiller may be sodium chloride, calcium chloride, or sodium sulfate. Whenthe calcination process is performed at 900 to 1,000° C., the filler maybe polymethyl methacrylate (PMMA), sodium chloride, calcium chloride, orsodium sulfate.

The preliminary secondary particle may be further subjected toultrasonic treatment and a drying process after water or a mixture ofwater and ethanol is added to remove the filler. Accordingly, thesecondary particle having a porosity in the range of 2% to 50% may beprepared.

A method of preparing a negative electrode active material according toyet another embodiment of the present invention is similar to theabove-described method of preparing a negative electrode active materialaccording to an embodiment of the present invention, except that thepreliminary primary particles are used as second particles to form asecondary particle further including the first particles and the secondparticles in Step 4. Specifically, not only the first particles but alsothe second particles may be aggregated together to form a secondaryparticle in Step 4.

In this case, the secondary particle may also be formed by aggregationsuch that the porosity between the first particles and the secondparticles is in the range of 2% and 50% in Step 4. Specifically, in Step4, a solution is prepared by containing the first particles, the secondparticles, and the filler in a solvent, and the solution is spray-driedto form a preliminary secondary particle in which the first particles,the second particles, and the filler are aggregated.

The filler is included to form a secondary particle such that theporosity between the first particles and the second particles is in therange of 2% to 50%, and the porosity may be controlled by adjusting theamount of the filler. The filler may be included in a volume ratio of1:0.01 to 1:0.43 with respect to the to the primary particles (the firstparticles and the second particles). Specific examples of the fillerinclude a metal, polymethyl methacrylate (PMMA), polystyrene beads,sodium chloride (NaCl), potassium chloride (KCl), sodium sulfate(Na₂SO₄), etc.

When the above-described calcination process is included in Step 4, thefiller may be sodium chloride, calcium chloride, or sodium sulfate. Whenthe calcination process is performed at 900 to 1,000° C., the filler maybe polymethyl methacrylate (PMMA), sodium chloride, calcium chloride, orsodium sulfate.

The preliminary secondary particle may be further subjected toultrasonic treatment and a drying process after water or a mixture ofwater and ethanol is added to remove the filler. Accordingly, thesecondary particle having a porosity in the range of 2% to 50% may beprepared.

Hereinafter, a lithium secondary battery according to yet anotherembodiment of the present invention will be described.

The lithium secondary battery according to yet another embodiment of thepresent invention includes an electrode assembly including a positiveelectrode, a negative electrode and a separator interposed between thepositive electrode and the negative electrode, and an electrolyte.

The positive electrode may include a positive electrode currentcollector, and a mixture of a positive electrode active material, aconductive material and a binder on the positive electrode currentcollector.

The positive electrode current collector is required to have highconductivity, allow the mixture to be easily adhered, and benon-reactive at a voltage range of a battery. Specific examples of thepositive electrode current collector include aluminum, nickel, alloysthereof, etc. The thickness of the positive electrode current collectormay be in the range of 3 to 500 μm.

Specific examples of the positive electrode active material includelithium cobalt oxides such as Li_(x1)CoO₂ (0.5<x1<1.3); lithium nickeloxide such as Li_(x2)NiO₂ (0.5<x2<1.3); lithium manganese oxides such asLi_(1+x3)Mn_(2-x)O₄ (0≤x3≤0.33), LiMnO₃, LiMn₂O₃, or Li_(x4)MnO₂(0.5<x4<1.3); lithium copper oxides such as Li₂CuO₂; lithium iron oxidessuch as LiFe₃O₄; lithium nickel cobalt manganese oxides such asLi[Ni_(xa)Co_(ya)Mn_(za)]O₂ (xa+ya+za=1, 0<xa<1, 0<ya<1, 0<za<1);lithium nickel cobalt aluminum oxides such asLi[Ni_(xb)Co_(yb)Al_(zb)]O₂ (xb+yb+zb=1, 0<xb<1, 0<yb<1, 0<zb<1);lithium vanadium compounds such as LiV₃O₈; nickel-site type lithiumnickel oxides such as LiNi_(1-x4)M_(x4)O₂ (M=Co, Mn, Al, Cu, Fe, Mg, Bor Ga, 0.01≤x4≤0.3); lithium manganese composite oxides such asLiMn_(2-x5)M_(x5)O₂ (M=Co, Ni, Fe, Cr, Zn or Ta, 0.01≤x5≤0.1) orLi₂Mn₃MO₈ (M=Fe, Co, Ni, Cu or Zn); LiMn₂O₄ in which a part of lithiumis substituted with an alkaline earth metal ions; disulfide compounds;vanadium oxides such as V₂O₅ or Cu₂V₂O₇; Fe₂(MoO₄)₃, etc. Morespecifically, the positive electrode active material may be a lithiumnickel cobalt manganese oxide such asLi[Ni_(xc)Co_(yc)Mn_(zc)]O₂(xc+yc+zc=1, 0.3≤xc≤0.4, 0.3≤yc≤0.4,0.3≤zc≤0.4) or a lithium nickel cobalt aluminum oxide such asLi[Ni_(xd)Co_(yd)Al_(zd)]O₂ (xd+yd+zd=1, 0.3≤xd≤0.4, 0.3≤yd≤0.4,0.3≤zd≤0.4). One or two or more thereof may be included in the positiveelectrode active material.

The conductive material is a material having electrical conductivitywithout causing a chemical change in the lithium secondary battery ofthe present invention. Specific examples of the conductive materialinclude conductive materials such as graphite such as natural graphiteor artificial graphite; carbon black such as carbon black, acetyleneblack, ketjen black, channel black, furnace black, lamp black, thermalblack, and the like; conductive fibers such as carbon fibers and metalfibers; metal powders such as carbon fluoride, aluminum, and nickelpowder; conductive whiskers such as zinc oxide, potassium titanate, andthe like; conductive metal oxides such as titanium oxide; polyphenylenederivatives, etc.

The binder is a component which assists in bonding between the positiveelectrode active material and the conductive material and in bonding tothe current collector. Specific examples of the binder includepolyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose(CMC), starch, hydroxypropyl cellulose, regenerated cellulose,polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene,an ethylene-propylene-diene monomer (EPDM) rubber, a hydrogenatednitrile butadiene rubber (HNBR), a sulfonated ethylene propylene diene,a styrene butadiene rubber (SBR), a fluorine rubber, various copolymers,etc.

The negative electrode includes a negative electrode current collectorand a negative electrode active material positioned on the negativeelectrode current collector.

The negative electrode current collector is required to have highconductivity, allow the negative electrode active material to be easilyadhered, and be non-reactive at a voltage range of a battery. Specificexamples of the negative electrode current collector include copper,gold, nickel, or alloys thereof.

The description of the negative active material is the same as that ofthe negative active materials of the above-described embodiments. Theseparator prevents a short circuit between the positive electrode andthe negative electrode, and provides a path for lithium ions. Aninsulating thin film having high ion permeability and mechanicalstrength may be used as the separator. Specific examples of theseparator include a polyolefin-based polymer membrane such aspolypropylene and polyethylene, or a multiple membrane thereof, amicroporous film, a woven fabric, a nonwoven fabric, etc. When a solidelectrolyte such as a polymer is used as an electrolyte to be describedlater, the solid electrolyte may also serve as a separator.

The electrolyte may be an electrolyte containing a lithium salt.Specific examples of the anion of the lithium salt include F⁻, Br⁻, I⁻,NO₃ ⁻, N(CN)₂ ⁻, BF₄ ⁻, ClO₄ ⁻, PF₆ ⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻,(CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, CF₃SO₃ ⁻, CF₃CF₂SO₃ ⁻, (CF₃SO₂)₂N⁻,(FSO₂)₂N⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, (SF₅)₃C⁻, (CF₃SO₂)₃C⁻,CF₃(CF₂)₇₅O₃ ⁻, CF₃CO₂ ⁻, SCN⁻, (CF₃CF₂SO₂)₂N⁻, etc. One or more thereofmay be included in the electrolyte.

The outer shape of the lithium secondary battery according to yetanother embodiment of the present invention is not particularly limited,and specific examples thereof include a cylindrical battery using a can,square, pouch or coin type batteries, etc.

The lithium secondary battery according to yet another embodiment of thepresent invention may be used in a battery cell used as a power sourcefor a small device, and may be preferably used as a unit battery in amiddle or large sized battery module including a plurality of batterycells. Specific examples of the middle or large sized battery moduleinclude an electric vehicle, a hybrid electric vehicle, a plug-in hybridelectric vehicle, a system for electric power storage or the like, butare not limited thereto.

Hereinafter, the present invention will be described in more detail withreference to the following examples. These examples are provided onlyfor illustration of the present invention and should not be construed aslimiting the scope and spirit of the present invention. Variousmodifications and alterations of the invention fall within the scope ofthe invention and the scope of the invention is defined by theaccompanying claims.

Example 1: Preparation of Negative Electrode Active Material

<Preparation of Core>

Silica oxides (SiO_(x), 0<x≤1) having an average particle size D₅₀ of 10μm were placed in a Spex mill 8000M, and 15 pieces of a sus ball mediawere added thereto, and milled for 2 hours to pulverize the particles toan average particle size D₅₀ of 1 μm to prepare a core.

<Preparation of Preliminary First Particle>

10 g of the core and 0.5 g of sucrose were added to 30 g of isopropanolto prepare a solution. The mixture was pulverized for 12 hours at a beadrotation rate of 1,200 rpm using beads formed of zirconia (averageparticle size: 0.3 mm). Subsequently, the mixture was dried in an ovenat 120° C. for 2 hours. The dried mixture was pulverized again in amortar and classified to form silicon particles mixed with sucrose. Theheat treatment was performed at 800° C. under a nitrogen atmosphere tocarbonize the sucrose to form a surface layer having a thickness of 2 nmto prepare preliminary first particles. The content of the surface layerwas 2.1 wt % based on the total weight of the core.

<Preparation of First Particle>

8 g of the preliminary first particles and 0.9 g of magnesium powderwere mixed in an argon gas atmosphere to prepare a mixed powder. Themixed powder was placed in a tube furnace and heated to 1030° C. at arate of 5° C./min in an argon gas atmosphere, followed by heating for 2hours. Thereafter, the temperature of the reaction furnace was loweredto room temperature, and the heat-treated mixed powder was taken out andwashed with 1M HCl for 1 hour while stirring. The washed mixed powderwas washed with distilled water while filtering, and then dried in anoven at 60° C. for 8 hours to prepare first particles. As a result ofanalyzing the prepared first particles, the content of magnesiumsilicate and magnesium oxide formed by oxidation of magnesium in thefirst particles was 15 wt % based on the total weight of the firstparticles, which was measured by quantitative analysis using X-raydiffraction (XRD).

<Preparation of Secondary Particle>

The solution containing the first particles and ethanol/water (volumeratio=1:9) in a volume ratio of 1:10 was stirred with a mechanicalhomogenizer at 10,000 rpm for 30 minutes to prepare a dispersionsolution for spray drying. The dispersion solution was spray-dried underthe conditions of an inlet temperature of 180° C., an aspirator of 95%,and a feeding rate of 12 of a mini spray-dryer (manufactured by BuchiCo., Ltd., model: B-290 Mini Spray-Dryer) to prepare preliminarysecondary particles, which were then transferred to an alumina boat. Thetemperature of a tube furnace equipped with a quartz tube having alength of 80 cm and an inner diameter of 4.8 cm was raised to 600° C. ata rate of 10° C./min, and then calcined while maintaining thetemperature for 2 hours to prepare secondary particles. The preparedsecondary particles had a porosity of 1% and an average particle sizeD₅₀ of 5 μm. The porosity was measured by a mercury porosimeter method.

Example 2: Preparation of Negative Electrode Active Material

<Preparation of Core and Preliminary First Particle>

The core and the preliminary first particle were prepared in the samemanner as in Example 1.

<Preparation of First Particle>

8 g of the preliminary first particles and 10 g of magnesium powder weremixed in an argon gas atmosphere to prepare a mixed powder. The mixedpowder was placed in a tube furnace and heated to 1030° C. at a rate of5° C./min in an argon gas atmosphere, followed by heating for 2 hours.Thereafter, the temperature of the reaction furnace was lowered to roomtemperature, and the heat-treated mixed powder was taken out and washedwith 1M HCl for 1 hour while stirring. The washed mixed powder waswashed with distilled water while filtering, and then dried in an ovenat 60° C. for 8 hours to prepare first particles. As a result ofanalyzing the prepared first particles, the content of magnesiumsilicate and magnesium oxide formed by oxidation of magnesium in thefirst particles was 51 wt % based on the total weight of the firstparticles, which was measured by quantitative analysis using X-raydiffraction (XRD).

<Preparation of Secondary Particle>

Secondary particles of Example 2 were prepared using the first particlesby the same method as a method of preparing the secondary particles ofExample 1. The prepared secondary particles had a porosity of 1% and anaverage particle size D₅₀ of 4 μm. The porosity was measured by amercury porosimeter method.

Example 3: Preparation of Negative Electrode Active Material

<Preparation of Core>

Silica oxides (SiO_(x), 0<x≤1) having an average particle size D₅₀ of 10μm were placed in a Spex mill 8000M, and 15 pieces of a sus ball mediawere added thereto, and milled for 4 hours to pulverize the particles toan average particle size D₅₀ of 0.4 μm to prepare a core.

<Preparation of Preliminary First Particle>

Preliminary first particles on which surface layers having a thicknessof 2 nm were formed were prepared using the core through the same methodas a method of preparing the preliminary first particles of Example 1.The content of the surface layer was 2.1 wt % based on the total weightof the core.

<Preparation of First Particle>

First particles were prepared using the preliminary first particlesthrough the same method as a method of preparing the first particles ofExample 1. As a result of analyzing the prepared first particles, thecontent of magnesium silicate and magnesium oxide formed by oxidation ofmagnesium in the first particles was 15 wt % based on the total weightof the first particles, which was measured by quantitative analysisusing X-ray diffraction (XRD).

<Preparation of Secondary Particle>

Secondary particles of Example 3 were prepared using the first particlesby the same method as a method of preparing the secondary particles ofExample 1. The prepared secondary particles had a porosity of 1% and anaverage particle size D₅₀ of 2 μm. The porosity was measured by amercury porosimeter method.

Example 4: Preparation of Negative Electrode Active Material

<Preparation of Core>

Silica oxides (SiO_(x), 0<x≤1) having an average particle size D₅₀ of 10μm were placed in a Spex mill 8000M, and 15 pieces of a sus ball mediawere added thereto, and milled for 4 hours to pulverize the particles toan average particle size D₅₀ of 0.4 μm to prepare a core.

<Preparation of Preliminary First Particle>

Preliminary first particles on which surface layers having a thicknessof 2 nm were formed were prepared using the core through the same methodas a method of preparing the preliminary first particles of Example 1.The content of the surface layer was 2.1 wt % based on the total weightof the core.

<Preparation of First Particle>

8 g of the preliminary first particles and 5 g of magnesium powder weremixed in an argon gas atmosphere to prepare a mixed powder. The mixedpowder was placed in a tube furnace and heated to 1030° C. at a rate of5° C./min in an argon gas atmosphere, followed by heating for 2 hours.Thereafter, the temperature of the reaction furnace was lowered to roomtemperature, and the heat-treated mixed powder was taken out and washedwith 1M HCl for 1 hour while stirring. The washed mixed powder waswashed with distilled water while filtering, and then dried in an ovenat 60° C. for 8 hours to prepare first particles. As a result ofanalyzing the prepared first particles, the content of magnesiumsilicate and magnesium oxide formed by oxidation of magnesium in thefirst particles was 55 wt % based on the total weight of the firstparticles, which was measured by quantitative analysis using X-raydiffraction (XRD).

<Preparation of Secondary Particle>

Secondary particles of Example 4 were prepared using the first particlesby the same method as a method of preparing the secondary particles ofExample 1. The prepared secondary particles had a porosity of 1% and anaverage particle size D₅₀ of 3 μm. The porosity was measured by amercury porosimeter method.

Example 5: Preparation of Negative Electrode Active Material

<Preparation of Core and Preliminary First Particle>

Preliminary first particles on which surface layers having a thicknessof 2 nm were formed were prepared through the same method as a method ofpreparing the core and the preliminary first particles of Example 1. Thecontent of the surface layer was 2.1 wt % based on the total weight ofthe core.

<Preparation of First Particle>

First particles were prepared using the preliminary first particlesthrough the method of preparing the first particles of Example 1. As aresult of analyzing the prepared first particles, the content ofmagnesium silicate and magnesium oxide formed by oxidation of magnesiumin the first particles was 15 wt % based on the total weight of thefirst particles, which was measured by quantitative analysis using X-raydiffraction (XRD).

<Preparation of Secondary Particle>

Secondary particles were prepared, through the first particles and thesecond particles, by using the preliminary first particles as the secondparticles. Specifically, after the first particles and the secondparticles were mixed in a weight ratio of 6:4, the solution containingthe mixture and ethanol/water (volume ratio=1:9) in a volume ratio of1:10 was stirred with a mechanical homogenizer at 10,000 rpm for 30minutes to prepare a dispersion solution for spray drying. Thedispersion solution was spray-dried under the conditions of an inlettemperature of 180° C., an aspirator of 95%, and a feeding rate of 12 ofa mini spray-dryer (manufactured by Buchi Co., Ltd., model: B-290 MiniSpray-Dryer) to prepare preliminary secondary particles, which were thentransferred to an alumina boat. The temperature of a tube furnaceequipped with a quartz tube having a length of 80 cm and an innerdiameter of 4.8 cm was raised to 600° C. at a rate of 10° C./min, andthen calcined while maintaining the temperature for 2 hours to preparesecondary particles. The prepared secondary particles had a porosity of1% and an average particle size D₅₀ of 5 μm. The porosity was measuredby a mercury porosimeter method

Example 6: Preparation of Negative Electrode Active Material

<Preparation of Core, First Particle and Second Particle>

The core, the first particle and the second particle (preliminary firstparticle) were prepared in the same manner as in Example 5.

<Preparation of Negative Electrode Active Material>

The secondary particles were prepared in the same manner as in Example 6except that the first particles and second particles were mixed in aweight ratio of 1.5:8.5. The prepared secondary particles had a porosityof 1% and an average particle size D₅₀ of 5 μm. The porosity wasmeasured by a mercury porosimeter method.

Comparative Example 1: Preparation of Negative Electrode Active Material

<Preparation of Core and Preliminary First Particle>

Preliminary first particles on which surface layers having a thicknessof 2 nm were formed were prepared through the same method as a method ofpreparing the core and the preliminary first particles of Example 1. Thecontent of the surface layer was 2.1 wt % based on the total weight ofthe core.

<Preparation of Secondary Particle>

Secondary particles were prepared by the same method as the method ofpreparing the secondary particles of Example 1 except that the firstparticles of Example 1 were not used and the preliminary first particleswere used. The prepared secondary particles had a porosity of 1% and anaverage particle size D₅₀ of 5 μm. The porosity was measured by amercury porosimeter method.

Comparative Example 2: Preparation of Negative Electrode Active Material

8 g of the preliminary first particles which were prepared in Example 1and 0.9 g of magnesium powder were mixed in an argon gas atmosphere toprepare a mixed powder. The mixed powder was placed in a tube furnaceand heated to 1030° C. at a rate of 5° C./min in an argon gasatmosphere, followed by heating for 2 hours. Thereafter, the temperatureof the reaction furnace was lowered to room temperature, and theheat-treated mixed powder was taken out and washed with 1M HCl for 1hour while stirring. The washed mixed powder was washed with distilledwater while filtering, and then dried in an oven at 60° C. for 8 hoursto prepare a negative electrode active material in the form of a singleparticle. As a result of analyzing the prepared negative electrodeactive material, the content of magnesium silicate and magnesium oxideformed by oxidation of magnesium in the negative electrode activematerial was 15 wt % based on the total weight of the negative electrodeactive material, which was measured by quantitative analysis using X-raydiffraction (XRD).

Examples 7 to 12 and Comparative Examples 3 and 4: Preparation ofBattery

<Preparation of Negative Electrode>

Each of the negative electrode active materials prepared in Examples 1to 6 and Comparative Examples 1 and 2, fine graphite as a conductivematerial, and polyacrylonitrile as a binder were mixed in a weight ratioof 7:2:1 to prepare 0.2 g of a mixture. 3.1 g of N-methyl-2-pyrrolidone(NMP) as a solvent was added to the mixture to prepare a negativeelectrode mixture slurry. The negative electrode mixture slurry wasapplied onto a copper (Cu) metal thin film as a negative electrodecurrent collector having a thickness of 20 μm and dried. Here, thetemperature of the circulating air was 80° C. Subsequently, theresultant was roll-pressed, dried in a vacuum oven at 130° C. for 12hours, and then punched to a circular shape of 1.4875 cm² to prepareeach of negative electrodes of Examples 7 to 12.

<Preparation of Battery>

Each of the negative electrodes thus prepared was cut into a circularshape of 1.4875 cm², which was used as a negative electrode, and alithium metal thin film cut into a circle of 1.4875 cm² was used as apositive electrode. A porous polyethylene separator was interposedbetween the positive electrode and the negative electrode, 0.5 wt % ofvinylene carbonate was dissolved in a mixed solution in which ethylmethyl carbonate (EMC) and ethylene carbonate (EC) were mixed in amixing volume ratio of 7:3, and then an electrolyte in which 1M LiPF₆was dissolved was injected thereto to prepare a lithium coin half-cell.

Experimental Example 1: Evaluation of Discharge Capacity, InitialEfficiency, Capacity Retention Ratio and Electrode Thickness ChangeRatio

The batteries of Examples 7 to 12 and Comparative Examples 3 and 4 werecharged and discharged to evaluate a discharge capacity, an initialefficiency, a capacity retention ratio and an electrode thickness changeratio, and the results are listed in the following Table 1.

Further, during the first and second cycles, charging and dischargingwas performed at 0.1 C, and during the 3rd through 49th cycles, chargingand discharging was performed at 0.5 C. At the 50th cycle, charging anddischarging was terminated in a charging state (lithium ions were put inthe negative electrode), and after disassembling the battery, athickness was measured and an electrode thickness change ratio wascalculated.

CC(constant current)/CV(constant voltage)(5 mV/0.005C currentcut-off)  Charging condition:

Discharging condition: CC(constant current) condition 1.5V

The discharge capacity (mAh/g) and initial efficiency (%) were derivedfrom the result after charging and discharging once. Specifically, theinitial efficiency (%) was derived by the following calculation.

Initial efficiency (%)=(discharge capacity after one discharge/onecharge capacity)×100

Each of the capacity retention ratio and the electrode thickness changeratio was derived by the following calculation.

Capacity retention ratio (%)=(49 times discharge capacity/one dischargecapacity)×100

Electrode thickness change ratio (%)=(final electrode thickness changeamount/initial electrode thickness)×100

TABLE 1 Electrode Discharge Initial Capacity thickness Active capacityefficiency retention change material (mAh/g) (%) ratio (%) ratio (%)Example 7 Example 1 1420 82.2 87.5 107 Example 8 Example 2 1400 84.2 87108 Example 9 Example 3 1350 81.5 87.3 105 Example 10 Example 4 130083.5 87.2 109 Example 11 Example 5 1508 80.08 88 105 Example 12 Example6 1520 75.5 87.0 115 Comparative Comparative 1550 74.0 86.5 123 Example3 Example 1 Comparative Comparative 1320 80.1 80 110 Example 4 Example 2

Referring to Table 1, it can be confirmed that Examples 7 to 12 in whichthe active material according to the present invention was used weresuperior in terms of the initial efficiency, capacity retention rate,and electrode thickness change ratio as compared to Comparative Example3. It can be seen that this was an effect obtained due to the core ofthe first particle containing a metal compound.

Further, it can be seen that Example 7 in which a negative electrodeactive material suitably containing 15 wt % of a metal compound in thecore was used had a higher discharge capacity and a higher capacityretention rate compared to Example 8 in which a negative active materialcontaining a metal compound at a high content of 51 wt % was used. Inthe case of Example 8, the metal doping amount for forming the metalcompound was excessively high, and thus the crystal size of Si in thenegative electrode active material was too large, and a part of themetal acted as an impurity, thereby adversely affecting battery life andlowering the capacity retention ratio. Further, Example 7 in which thenegative electrode active material of Example 1 having a core with asuitable size of 1 μm was used had higher discharge capacity, initialefficiency, and capacity retention ratio compared to Example 9 in whichthe negative electrode active material of Example 3 having anexcessively small core with a size of 0.4 μm was used.

This is because the irreversible reaction is increased due to anincrease in the specific surface area when a small-sized core is used.

Examples 13 to 17 and Comparative Examples 5 and 6: Preparation ofBattery

<Preparation of Negative Electrode>

A mixed negative electrode active material prepared by mixing each ofthe negative electrode active materials prepared in Examples 1 to 5 andComparative Examples 1 and 2 with graphite (natural graphite) at aweight ratio of 1:9, carbon black as a conductive material,carboxylmethyl cellulose (CMC), and a styrene butadiene rubber (SBR)were mixed at a weight ratio of 95.8:1:1.7:1.5 to prepare 5 g of amixture. 28.9 g of distilled water was added to the mixture to prepare anegative electrode mixture slurry. The negative electrode mixture slurrywas applied onto a copper (Cu) metal thin film as a negative electrodecurrent collector having a thickness of 20 μm and dried. Here, thetemperature of the circulating air was 60° C. Subsequently, theresultant was roll-pressed, dried in a vacuum oven at 130° C. for 12hours, and then punched to a circular shape of 1.4875 cm² to prepareeach of negative electrodes of Examples 13 to 17 and ComparativeExamples 5 and 6.

<Preparation of Battery>

Each of the negative electrodes thus prepared was cut into a circularshape of 1.4875 cm², which was used as a negative electrode, and alithium metal thin film cut into a circle of 1.4875 cm² was used as apositive electrode. A porous polyethylene separator was interposedbetween the positive electrode and the negative electrode, 0.5 wt % ofvinylene carbonate was dissolved in a mixed solution in which ethylmethyl carbonate (EMC) and ethylene carbonate (EC) were mixed in amixing ratio of 7:3, and then an electrolyte in which 1M LiPF₆ wasdissolved was injected thereto to prepare a lithium coin half-cell.

Experimental Example 2: Evaluation of Initial Efficiency, CapacityRetention Ratio and Electrode Thickness Change Ratio

The batteries of Examples 13 to 17 and Comparative Examples 5 and 6 werecharged and discharged to evaluate an initial efficiency, a capacityretention ratio, and an electrode thickness change ratio, and theresults are listed in the following Table 2. FIG. 7 shows the normalizedcapacity for each cycle number of Examples 13 to 16 and ComparativeExamples 5 and 6.

Further, during the first and second cycles, charging and dischargingwas performed at 0.1 C, and during 3rd through 49th cycles, charging anddischarging was performed at 0.5 C. At 50th cycle, charging anddischarging was terminated in a charging state (lithium ions were put inthe negative electrode), and after disassembling the battery, athickness was measured and an electrode thickness change ratio wascalculated.

CC(constant current)/CV(constant voltage)(5 mV/0.005C currentcut-off)  Charging conditions:

Discharging conditions: CC(constant current) condition 1.5V

The initial efficiency (%) was derived from the result after chargingand discharging once. Specifically, the initial efficiency (%) wasderived by the following calculation.

Initial efficiency (%)=(discharge capacity after one discharge/onecharge capacity)×100

Each of the capacity retention ratio and the electrode thickness changeratio was derived by the following calculation.

Capacity retention ratio (%)=(49 times discharge capacity/one dischargecapacity)×100

Electrode thickness change ratio (%)=(electrode thickness changeamount/initial electrode thickness)×100

TABLE 2 Electrode Initial Capacity thickness efficiency retention changeratio Active material (%) ratio (%) (%) Example 13 Example 1 Graphite89.4 90.2 53.0 Example 14 Example 2 Graphite 90.2 89.8 53.2 Example 15Example 3 Graphite 89.3 89.5 53.2 Example 16 Example 4 Graphite 90.189.2 53.3 Example 17 Example 5 Graphite 89.0 89.0 52.5 ComparativeComparative Graphite 86.1 88.8 53.4 Example 5 Example 1 ComparativeComparative Graphite 88.9 87.5 55.0 Example 6 Example 2

Referring to Table 2 and FIG. 7, it was confirmed that the batteries ofExamples 13 to 17 according to the present invention were superior ininitial efficiency and capacity retention ratio compared to thebatteries of Comparative Examples 5 and 6. Further, in the case ofExamples 13 to 17, it was confirmed that the performance was superior interms of the initial efficiency, capacity retention rate, and electrodethickness change ratio, compared to Examples 7 to 12. Accordingly, itcan be seen that, when the active material of the present invention isused together with graphite, more excellent effects can be obtained.

  Description of Reference Numerals 110: first particle 111: first core112: first surface layer 113: metal compound 120: second particle 121:second core 122: second surface layer 130: carbon layer 140: crystallinecarbon-based material 200, 210, 220, 230, 240 and 250: secondaryparticle

1. A negative electrode active material, comprising a secondary particleincluding a first particle which is a primary particle and a secondparticle which is a primary particle, wherein the first particleincludes a first core, and a first surface layer which is disposed on asurface of the first core and contains carbon, and the first coreincludes: one or more of silicon and a silicon compound; and a metalcompound which includes one or more of a metal oxide and a metalsilicate, wherein the secondary particle further includes a secondparticle which is a primary particle, the second particle includes asecond core and a second surface layer which is disposed on a surface ofthe second core and contains carbon, and the second core includes one ormore of silicon and a silicon compound.
 2. The negative electrode activematerial according to claim 1, wherein the metal compound is doped in anamount of 1 to 50 wt % based on the total weight of the first particle.3. The negative electrode active material according to claim 1, whereina weight ratio of the first particle and the second particle is in arange of 1:0.25 to 1:4.
 4. The negative electrode active materialaccording to claim 1, wherein an average particle size D₅₀ of each ofthe first core and the second core is in a range of 0.5 to 20 μm.
 5. Thenegative electrode active material according to claim 1, wherein thesilicon included in each of the first core and the second core includesone or more of an amorphous silicon and a crystalline silicon having acrystal size of more than 0 to 30 nm or less.
 6. The negative electrodeactive material according to claim 1, wherein the silicon compoundincluded in each of the first core and the second core is a siliconoxide (SiO_(x), 0<x<2) in which silicon is dispersed in a silicondioxide (SiO₂) matrix.
 7. The negative electrode active materialaccording to claim 1, wherein the first core and the second core is aporous core including a plurality of pores.
 8. The negative electrodeactive material according to claim 7, wherein an internal porosity ofthe porous core is in a range of 5% to 90% based on the total volume ofthe porous core.
 9. The negative electrode active material according toclaim 1, wherein the metal oxide includes an oxide of one or more metalsselected from the group consisting of lithium (Li), magnesium (Mg),aluminum (Al), calcium (Ca), and titanium (Ti).
 10. The negativeelectrode active material according to claim 1, wherein the metalsilicate includes a silicate of one or more metals selected from thegroup consisting of lithium (Li), magnesium (Mg), aluminum (Al), calcium(Ca), and titanium (Ti).
 11. The negative electrode active materialaccording to claim 1, wherein a thickness of the first surface layer andthe second surface layer is in a range of 1 to 100 nm.
 12. The negativeelectrode active material according to claim 1, wherein the secondaryparticle has an average particle size D₅₀ in a range of 2 to 50 μm. 13.The negative electrode active material according to claim 1, wherein thenegative electrode active material further comprises a carbon layerwhich is disposed on a surface of the secondary particle and containscarbon.
 14. The negative electrode active material according to claim13, wherein a thickness of the carbon layer is in a range of 5 to 100nm.
 15. The negative electrode active material according to claim 1,wherein the secondary particle further includes a crystallinecarbon-based material which is a primary particle.
 16. The negativeelectrode active material according to claim 1, wherein the negativeelectrode active material further comprises a graphite-based activematerial particle.
 17. A negative electrode, comprising the negativeelectrode active material according to claim
 1. 18. A lithium secondarybattery, comprising the negative electrode according to claim 17.